EP2069446A1 - Color change cyanoacrylate adhesives - Google Patents
Color change cyanoacrylate adhesivesInfo
- Publication number
- EP2069446A1 EP2069446A1 EP07841916A EP07841916A EP2069446A1 EP 2069446 A1 EP2069446 A1 EP 2069446A1 EP 07841916 A EP07841916 A EP 07841916A EP 07841916 A EP07841916 A EP 07841916A EP 2069446 A1 EP2069446 A1 EP 2069446A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cyanoacrylate
- acid
- dye
- based adhesive
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
Definitions
- Cyanoacrylate adhesives also known as "super glues," are a versatile family of adhesives known to cure in seconds and provide strong adhesion to a wide variety of surfaces. In spite of these noteworthy attributes, several issues exist that limit the popularity of this adhesive class with consumers.
- cyanoacrylate adhesives bond instantly with skin. This issue is compounded by the fact that cyanoacrylate adhesives are usually colorless and difficult to observe when applied to a substrate. The inability of the end- user to observe where the adhesive is (or is not), as well as whether the adhesive is cured, often leads to unintended bonding of skin to itself or other substrates.
- Some cyanoacrylate adhesives are lightly tinted to provide the end-user some ability to discriminate where the adhesive has and has not been applied. However, these color tints are often so light that a thinly applied adhesive layer is not perceptible. Increasing the intensity of color tint so that the thinly applied adhesive layer is perceptible, results in the cured adhesive remaining visible on the completed project which may be objectionable to the consumer.
- cyanoacrylate-based adhesive compositions include a cyanoacrylate monomer and a bleachable dye such as, for example, a Michler's hydrol cation or Michler's hydrol cation derivative, that provides a stable color to the uncured cyanoacrylate-based adhesive when paired with a non- nucleophilic anion.
- the method includes combining an appropriately stabilized cyanoacrylate monomer with a bleachable dye such as, for example, a Michler's hydrol cation or derivatized Michler's hydrol cation paired with a non-nucleophilic anion to form a dye pair.
- the stabilized cyanoacrylate monomer and dye pair forms a cyanoacrylate-based adhesive composition.
- the dye pair provides a stable color to the cyanoacrylate-based adhesive composition.
- the present disclosure is directed to color change cyanoacrylate adhesives and methods of using the same.
- the cyanoacrylate adhesive is colored in the uncured state and becomes colorless or light-colored upon cure.
- the cyanoacrylate adhesive is a first color in the uncured state and changes to a second color upon cure.
- These color change adhesives can allow the end- user to easily observe the lay of the adhesive as it is dispensed, and additionally, affords a means of visually assessing uniformity of bond lines, as well as determining where excess adhesive has been applied.
- These color change adhesives can allow the end-user a means of indicating the state-of-the-cure of the adhesive.
- the adhesive is colored, it is not cured, and accordingly, when said adhesive is fully cured, it is colorless or lightly colored. Normally if exposed adhesive is colorless or lightly colored it is sufficiently cured so that it may be touched without fear of bonding to the skin. While the present invention is not so limited, an appreciation of various aspects of the invention will be gained through a discussion of the examples provided below.
- polymer will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend.
- alkyl refers to a straight or branched chain monovalent hydrocarbon radical optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N. Alkyl groups generally include those with one to twenty atoms or from one to ten atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition.
- Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
- alkyl as used herein include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, and isopropyl, and the like.
- stable color will be understood to mean that a color or color intensity that visually persists for at least 14 days as measured by the test method described in the Examples herein.
- a flowable cyanoacrylate adhesive is said to possess a "stable color” if the color or color intensity (e.g., blue color) visually persists for at least 14 days in a sealed container.
- the samples remain usefully colored for a period of at least six months, or at leastl year, or at least 2 years.
- the bleachable dyes of the present invention tend to bleach irreversibly when formulated in color change cyanoacrylate compositions.
- the cyanoacrylate-based adhesive composition described herein includes a cyanoacrylate monomer and a bleachable dye cation paired with a non-nucleophilic anion that provides the bleachable dye with a stable color. As this cyanoacrylate-based adhesive cures, it becomes colorless or lightly colored.
- the bleachable dye cation paired with a non-nucleophilic anion is blended with the cyanoacrylate monomer prior to being applied to a substrate.
- the bleachable dye cation paired with a non-nucleophilic anion is not blended with the cyanoacrylate monomer before the cyanoacrylate monomer is disposed on a substrate.
- the bleachable dye cation paired with a non-nucleophilic anion can be disposed on the substrate and then the cyanoacrylate monomer is disposed on the bleachable dye cation paired with a non-nucleophilic anion.
- the bleachable dye cation or cations can be chosen to produce any color, as desired.
- the bleachable dye cation produces a blue or deep blue color.
- the bleachable dye cation is formed from a Michler's hydrol (i.e., 4,4'-bis(dimethylamino)benzhydrol) or a derivative thereof.
- Michler's hydrol or 4,4'-bis(dimethylamino)benzhydrol is commercially available (from Sigma- Aldrich, St. Louis, MO 63103) and has the following chemical structure:
- Michler's hydrol is a dye base and is colorless in its free (pure) form, and because this dye base by virtue of its amine substituents is nucleophilic, and as such will cause immediate polymerization of cyanoacrylate monomer, it is acidified prior to introduction into the cyanoacrylate described herein.
- Michler's hydrol cation provides a blue (cyan) color: the color intensity varying with the acidified dye concentration. Selection of the appropriate acid stabilizer or non-nucleophilic anion to maintain dye (color) stability upon aging is described below.
- Michler's hydrol cation is a dye that is degraded ( e -g- > bleached) concomitant with curing of the cyanoacrylate adhesive composition.
- Derivatized Michler's hydrol can be used for the bleachable dye cation.
- Useful derivatized Michler's hydrols include, for example, the following molecules: bis[4-(4-morpholinyl)phenyl]methanol (CAS#123344-13-8) having a chemical structure:
- N-[bis(4-dimethylaminophenyl)methyl]morpholine (CAS#21295-86-3) having a chemical structure:
- the bleachable dye cation can be present in the cyanoacrylate adhesive in any useful amount. In many embodiments, the bleachable dye cation can be present in the cyanoacrylate adhesive in an amount from 1 ppm or greater, or 10 ppm or greater, or 50 ppm or greater, or 100 ppm or greater, or 250 ppm or greater, or 500 ppm or greater, or 1000 ppm or greater. In some embodiments, the bleachable dye cation can be present in the cyanoacrylate adhesive in an amount from 1 ppm to 1000 ppm, or from 10 to 500 ppm, or from 1 to 100 ppm.
- the non-nucleophilic anion is typically derived from acids of high strength.
- the strength of such acids is often classified by means of Acidity Indicators, i.e., members of a series of increasingly weak nitrated aniline bases that provide a readily measured color change upon protonation.
- Acidity Indicators i.e., members of a series of increasingly weak nitrated aniline bases that provide a readily measured color change upon protonation.
- the accepted measure of the "strength" of aqueous acidic solutions is pH, the negative logarithm of the hydrogen ion concentration (or activity), and PK A , which similarly is the negative logarithm of the ionization constant K A , in aqueous solution, of weak to moderately strong acids.
- Hammett Acidity Function scale was created (L. P. Hammett & A.J. Deyrup, J Amer. Chem. Soc, 54 2721, 4239 (1932), 55 1900 (1933)). Its numerical scale was provided by stepwise dilution of each acid by water until the composition fell within the measurable pH range, thus it was termed an extension of the pH scale. Color-indicating very weak bases were provided, for which the protonated forms had non-aqueous pH- like behavior that could be inter-related by stepwise overlap. While useful, the H 0 scale provides no common non-aqueous medium for comparisons, as each anhydrous acid differs in solvent properties. Nearly all common "good" solvents are protonated by, or are reactive toward, very strong acids. Furthermore, to retain both neutral and ionic species in solution, a relatively high dielectric constant is accepted as necessary.
- the Hammett Acidity Function is applied to pure or nearly pure acids, a situation extremely different from the use in solution in a cyanoacrylate monomer. It is appropriate therefore to evaluate acid strengths in a polar organic solvent by a means analogous to ordinary aqueous buffer systems, which depend on the strength of the acids employed.
- Anhydrous "Sulfolane” (tetramethylene sulfone; tetrahydrothiophene-1,1- dioxide; CAS RN 126-33-0), is an acid-inert non-dissociating good solvent of high dielectric constant, 44, (E.M. Arnett & CF. Douty, J Amer. Chem. Soc, 86409 (1964)), and has the further advantage that the melting point is a sensitive measure of its water content (R.L. Burwell Jr & CH. Langford, J Amer. Chem. Soc, 81 3799 (1959)).
- Strength of an acid buffer of any composition may for simplicity be expressed by means of the ratio of molar extinction coefficients, ⁇ , and ⁇ *, where ⁇ is the molar extinction coefficient of an Acidity Indicator, I, in the acid-free solvent, sulfolane, and ⁇ * is the apparent molar extinction coefficient of that Acidity Indicator in a buffered test solution (as described in the Test Methods section) according to the following equations:
- E ( ⁇ - ⁇ *)/ ⁇ (for a specified Acidity Indicator, I)
- E expresses the strength of the acid itself.
- IH + the strength of the conjugate acid
- the Strength Ratio, E defined as ( ⁇ - ⁇ *)/ ⁇ , for a chosen 1 : 1 buffer system in the sulfolane solvent described above, is greater than 0.1 (corresponding to "PK A " ⁇ +2.0), preferably greater than 0.25 (corresponding to "PK A " ⁇ +1.5) when the indicator I is 4-methoxy-2-nitroaniline.
- the acid Strength Ratio E is greater than 0.2, preferably greater than 0.5 (corresponding to "PK A " ⁇ -1.0), when the indicator is 4-chloro-2-nitroaniline, or more preferably greater than 0.50 (corresponding to "PK A " ⁇ -2.3) when the indicator is 2-chloro-6-nitroaniline, or even more preferably greater than 0.5 (corresponding to "PK A " ⁇ -5.4) when the indicator is 2,6-dinitroaniline.
- the mathematically equivalent Acid Strength measure, "PK A ", applicable to all buffer ratios, is described in the Test Methods section. It enables the Strength Ratio, E, to be ascertained by means of titration.
- Carbon-acids differ qualitatively in being extremely much weaker than acids bearing the acidic hydrogen on, for example, oxygen or nitrogen, as is well established in the scientific literature. It is unusual for a carbon-acid to possess sufficient acid strength to be measurable using the nitrated aniline Acidity Indicators utilized herein. For a carbon-acid to be this strong it is necessary that its anion be non-nucleophilic. As compared to the strong non-carbon-acids which homopolymerize epoxy compounds, the observation that these relatively weaker carbon-acids also homopolymerize epoxy compounds demonstrates the comparably non-nucleophilic nature of their anions.
- the non-nucleophilic anion can include an ⁇ , ⁇ -highly fluorinated or perfluorinated(Ci-C 8 )alkylsulfonate anion.
- the non-nucleophilic anions include those derived from bis( ⁇ , ⁇ -highly fluorinated or perfluorinated- sulfonyl)methane, tris( ⁇ , ⁇ -highly fluorinated or perfluorinated-alkylsulfonyl)methane, bis( ⁇ , ⁇ -highly fluorinated or perfluorinated-alkylsulfonyl)imide, or mixtures thereof.
- the non-nucleophilic anion may be formed from trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, fluorosulfonic acid, bis(trifluoromethanesulfonyl)methane (methylene disulfone), bis(trifluoromethanesulfonyl)imide (imide acid), bis(pentafluoroethanesulfonyl)imide (ethylimide acid), tris(trifluoromethanesulfonyl)methane (methide acid), boron trifluoride bis-acetic acid, and other boron trifluoride complexes such as the etherate, methanol, propanol, and tetrahydrofuran derivatives.
- the non-nucleophilic anion is formed from trifluoromethanesulfonic acid, methide acid, boron trifluoride methanol, boron trifluoride bis-acetic acid, imide acid, and/or ethylimide acid. In certain preferred embodiments, the non-nucleophilic anion is formed from imide acid, boron trifluoride bis-acetic acid, and/or methide acid.
- the non-nucleophilic anion can be present in the cyanoacrylate adhesive in any useful amount.
- the acid of the non-nucleophilic anion can be present in the cyanoacrylate adhesive in an acid/dye mol ratio from 1 to 5, or from 1 to 2.5.
- the acid of the non-nucleophilic anion can be present in the cyanoacrylate adhesive in an acid/dye mol ratio from 1 to 5, or from 1 to 3, or from 1.5 to 2.5.
- the presence of lesser amounts (equivalents) of certain nucleophilic anions may sometimes be tolerated.
- Cyanoacrylate adhesives described herein include, for example, 2-cyanoacrylates such as, for example, methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, propyl-2- cyanoacrylate, isopropyl-2-cyanoacrylate, butyl-2-cyanoacrylate, isobutyl-2- cyanoacrylate, amyl-2-cyanoacrylate, hexyl-2-cyanoacrylate, cyclohexyl-2- cyanoacrylate, octyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, allyl-2- cyanoacrylate, propargyl-2-cyanoacrylate, phenyl-2-cyanoacrylate, benzyl-2- cyanoacrylate, methoxyethyl-2-cyanoacrylate, ethoxyethyl-2-cyanoacrylate, tetrahydrofulfuryl-2-cyanoacrylate, 2-chloro
- the cyanoacrylate-based adhesive compositions described herein are liquid or gels (if a sufficient amount of thickener is combined) prior to curing.
- the liquid or flowable cyanoacrylate-based adhesive compositions have a viscosity in a range from 1 to 5000 cP, as desired.
- the color change 2-cyanoacrylate-based adhesive composition described herein can optionally include an additional colorant, a radical polymerization stabilizer, a thickener, a curing accelerator, a crosslinker, a plasticizer and/or a thixotropic agent, as desired.
- all additives should be substantially anhydrous and free of nucleophilic compounds that may be deleterious to the bleachable color stability, the viscosity stability or both.
- the selection of the acidic compounds influence curing speed and product life of 2-cyanoacrylate-based compositions. Thus, selection of their suitable amounts to be added and combination can be determined by taking into account target curing performance, product life, color change performance and various other aspects.
- the additional colorant can be provided to achieve change in colors from a first colored state to a second colored state as the color change cyanoacrylate-based adhesive progresses from an uncured state to a cured state.
- the additional colorant can be any useful dye or pigment.
- the additional colorant is an indicator dye (not a bleachable dye such as Michler's hydrol or derivative) that can further change color as the cyanoacrylate-based adhesive progresses from an uncured state to a cured state.
- the additional colorant includes two or more pigments or dyes, depending on a desired color (in the cured or uncured state).
- the change in color of the cyanoacrylate-based adhesive from a first colored uncured state to a final colored cured state, or from a first colored uncured state to a final colorless cured state can be used to indicate the progress of the curing reaction or change in the cyanoacrylate-based adhesive.
- Visual color standards may be prepared and provided as a reference to the reaction progress. For example, a simple series of three printed color-matched dots that diminish in intensity as the concentration of acidified Michler's hydrol cation in the curing adhesive diminishes might be useful in determining whether the adhesive was curing properly, and furthermore aid in identifying whether the initial composition was sufficiently unpolymerized to be a useful adhesive composition.
- the radical polymerization stabilizer can include hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. In some embodiments, the radical polymerization stabilizer can be present in the range of 1 ppm by weight to 1% by weight.
- anion polymerization accelerators can be added to uncured cyanoacrylate adhesives, which include polyalkylene oxides and their derivatives, crown ethers and their derivatives, silacrown ethers and their derivatives, calixarene derivatives, thiacalixarene derivatives and the like, and combinations or blends of any of the aforementioned classes of accelerators.
- Some useful accelerants are disclosed in U.S. Patent No. 6,835,789 and incorporated herein to the extent it does not conflict. In some embodiments, the accelerant is present in the range from 200 to 5000 ppm.
- Nucleophilic polymerization accelerators e.g., amines such as N,N-dimethyl-p- toluidine solutions may also be applied to adherend surfaces prior to application of an uncured cyanoacrylate adhesive in order to accelerate cure of the adhesive.
- Thermal performance of cyanoacrylate adhesives is typically improved by the addition of crosslinkers, i.e., multi-functional monomers which upon or subsequent to cure crosslink the polymerizing adhesive.
- Useful crosslinkers may include biscyanoacrylates, allyl-2-cyanoacrylate, propargyl-2-cyanoacrylate, multi-functional acrylates and (meth)acrylates, and combinations of the aforementioned.
- the thickener can include viscosity modifiers, gel formers, thixotropic, and/or polymeric additives such as, for example, polymethylmethacrylate (PMMA), methyl methacrylate/acrylate copolymers, methyl methacrylate/methacrylate copolymers, cellulose derivatives, fumed silica, hydrophobic silica, and the like.
- PMMA polymethylmethacrylate
- the thickener can be added in the range of 0.1 to 20% by weight.
- the thickener can be added to provide a viscosity in a range from 5 to 5000 cP.
- the thickener can be added to provide a viscosity in a range from 2500 to 100,000 cP.
- PMMA and fumed silica are combined in the composition to form a cyanoacrylate adhesive gel.
- the plasticizer can be added to adjust modulus of the adhesive from a rigid adhesive to a toughened or flexible adhesive.
- Plasticizers can include, for example, phthalate esters, citrate esters, glycerol triacetate, specific multifunctional (meth)acrylates and the like.
- the plasticizer can be added in the range of 0.01 to 30% by weight.
- perfumes, fillers, crosslinking agents, polymerization initiators, organic solvents or the like can optionally be added, as desired.
- Set time was determined by depositing a single drop of cyanoacrylate adhesive (hereinafter "CA") on a glass microscope slide, overlapping a second slide atop the first, and applying modest finger pressure on the top slide in the bonding region to create a thin glue line.
- CA cyanoacrylate adhesive
- a stop watch is started. While holding the 1st slide, the 2nd slide non-bonded end is moved slowly from side to side over a small range of motion, of no more than 30 degrees, to determine when it can no longer be moved. When slide 2 can no longer be moved, the time on the stopwatch is recorded as the set time.
- a quantitative color assessment was performed to determine if changes occurred in sample color over time. This quantitative assessment was conducted by comparing the example to known colorimetric standards consisting of aqueous methylene blue solutions (preferably acidified by acetic acid) at concentrations of 2.0 x 10 "4 M, 1.5 x 10 "4
- the objective of this test method is to establish the strength of the acid being tested, as expressed, for example, in a half-neutralized "buffer” solution in purified sulfolane (tetramethylene sulfone), from which the strength is revealed by UV-Vis spectrometry to determine degree of protonation of an Acidity Indicator, I, and expressed relative to it as the Strength Ratio, E. More generally the mathematically equivalent Acid Strength, "PK A ", available from buffers of all ratios, or by titration, may be used to calculate the Strength Ratio. Purification of Sulfolane
- sulfolane having a mp of at least 26.0 0 C, or preferably at least 28.0 0 C, or more preferably greater than or equal to 28.4°C relative to the mp of
- the supernatant liquid is decanted into a 500 ml Erlenmeyer flask with pressure- relief stopper, and to it is added 15 g of a previously-prepared drying mixture, which had been made at least one day earlier by shaking together in a well sealed bottle equal weights of phosphorus pentoxide and 100-200 mesh silica gel that had been dried at 170 0 C overnight.
- the flask of sulfolane and drying mixture is heated for at least 1 week on a hot plate at 100 0 C and soon turns to an amber-brown color. It is then cooled and the very dark liquid decanted into a 250 ml distilling flask.
- an ordinary oil pump capable, with liquid nitrogen trap, of exhausting the system to 0.05 Torr. is needed, to enable sulfolane to distill at 68- 75°C, as much higher pressure and temperature may produce discoloration.
- the system pressure is continuously monitored by means of an electronic vacuum gauge reading with reasonable precision from 0.010 Torr. to 1.0 Torr. Water flow through the condenser must be restricted, as the distillate will freeze and plug it below 30 0 C, with hazardous consequences.
- Distillation should become relatively stable around 73°C/0.10 Torr., and a large center cut of 130-150 g should be taken at 72°C/0.090 Torr. to 68°C/0.050 Torr.
- This cut upon crystallization in its ca. 150 mL receiver flask, should upon warming show melting of its last crystals at 2 0 C, or preferably 1.5 0 C, or more preferably 1°C below the melting point of 99.999% gallium metal, 29.765°C, one of several pure-metal melting points that officially define the Celsius temperature scale, as explained by H. Preston- Thomas et al, Metrologia 27 3 (1990).
- the literature melting point, 28.86 0 C given without reference to one another by S. F. Birch and D.
- Sulfolane has a low heat of fusion, as given by R.L Burwell Jr. and CH. Langford, J. Amer. Chem. Soc, 81 3799 (1959), and therefore has an extremely large freezing point depression, thus providing an upper limit on water content, increasing by
- sulfolane does not have to be treated with excessive care, as it is virtually nonvolatile at atmospheric pressure, thus cannot condense moisture by evaporative cooling, nor lose weight by evaporation, when handled briefly in open vials. Little or no water is absorbed from the air, as shown by slow change at the 0.01 mg level of weight of an open vial of sulfolane on the balance.
- the needed density of the reference solution is most easily established by use of a small Ostwald-Sprengel pycnometer of approximately 0.5 to 2 ml volume which has been calibrated against water. To fill the pycnometer by suction its tip may be dipped into the test solution in the cell after the spectral measurement has been made.
- the existing impurity is normally water.
- the effective purity, TVT may be estimated by (gravimetric) titration in anhydrous sulfolane with an anhydrous weighable base. Note that unknown but limited amounts of water present in the sulfolane will partially “neutralize” a very strong acid and modify the titration and "PK A " calculation accordingly, but will not change the validity of the resulting "PK A ".
- Imidazole readily soluble in sulfolane, is normally an excellent choice as the titration or buffer-making base. Results agree with those from ethyldiisopropylamine, despite the latter's volatility and its very limited solubility in sulfolane. They also agree with those from the additive bases, CF 3 SOs-Na + and CF 3 SO 3 " (Bu 4 N) + , these of course being limited to CF 3 SO 3 H. In view of its low molecular weight, a 1.000 molal concentrate of imidazole in sulfolane is recommended.
- Acidity measurements are best made with F and B about 0.1 m or lower, for solubility reasons and to keep the sulfolane, as the solvent medium, in great excess. At greater dilution of very strong acids, extremely dry sulfolane is needed to minimize interference.
- the Strength Ratio, E defined as ( ⁇ - ⁇ *)/ ⁇ for a chosen 1 :1 buffer system, HA: A " , plus indicator IH + :I, in sulfolane solvent, is not correct unless the true concentrations of HA and A " are known to be equal. This is best ascertained and verified by gravimetric-spectrophotometric titration, to determine the true concentration of the strong acid component in the measurement sample, as described below.
- a stock solution is made from 0.28133 g of pure, colorless sublimed crystals of methylene disulfone, MDS, and sulfolane to total 9.99476 g.
- MDS methylene disulfone
- sulfolane sulfolane
- the indicator concentrate is made by dissolving 6.07 mg of 4-Methoxy-2- nitroaniline (molecular wt.
- PROl refers to 2-ethylcyanoacrylate, 100 cP, super fast cure, 10-30 second set time, available from Chemence, Inc., Alpharetta, GA 30005.
- SB20 refers to 2-ethylcyanoacrylate, 5 cP, ethyl hybrid, 0-20 sec set time, high strength bonds on acidic surfaces, available from Chemence, Inc., Alpharetta, GA 30005.
- SB 14 refers to 2-ethylcyanoacrylate, 100 cP, 10-60 second set time, high strength bonds on plastic and rubber, available from Chemence, Inc., Alpharetta, GA 30005.
- RX-100 refers to 2-ethylcyanoacrylate, 100 cP, non-surface sensitive, 10-30 sec set time, available from Pacer Technology, Collinso Cucamonga, CA 91730.
- TX-100 refers to 2-ethylcyanoacrylate, 100 cP, 10-30 sec set time, available from Pacer Technology, Collinso Cucamonga, CA 91730.
- NOlOO refers to 2-methoxy-ethoxy- ⁇ -cyanoacrylate, 100 cP, no odor, no frost, 30-50 sec set time, available from Pacer Technology, Collinso Cucamonga, CA 91730.
- HC 150 refers to 2-isopropylcyanoacrylate, 150 cP, low chlorosis, high clarity, better moisture resistant than ethylcyanoacrylates, 10-30 sec set time, available from Pacer Technology, Collinso Cucamonga, CA 91730.
- Scotchweld cyanoacrylate adhesives available from 3M, Maplewood, MN 55144 are listed in Table E below:
- ScotchTM Super Glue Liquid catalog number ADl 10, 2-ethylcyanoacrylate, available from 3M, St Paul, MN, 55144.
- Trifluoromethanesulfonylamide "sulfonyl amide”, synthesized using the procedures disclosed in US 5,874,616. Tris(trifluoromethanesulfonyl)methane, "methide acid”, 58.4 % solids aqueous, synthesized using the procedures disclosed in US 5,554,664.
- Dye base concentrate A - 9 pt methyl acetate and 1 pt Michler's hydrol.
- MSA Concentrate - solution consisting of 1.8 pt PROl and 0.2 pt methanesulfonic acid.
- TFMSA Concentrate - solution consisting of 1.8 pt PROl and 0.2 pt triflic acid (i.e., trifluoromethanesulfonic acid).
- Microscope slide VWR Cat # 48300-025, selected precleaned, 25 x 75 x 1 mm thick.
- LexanTM polycarbonate sheeting 2.9 mm thick, cut into 26.5 mm x 103 mm coupons, available from GE Plastics, Pittsfield, MA 01201.
- ProntoTM Surface Activator acetone solution of N,N-dimethyl-p-toluidine, available from 3M, St. Paul, MN 55144.
- a variety of commercially available cyanoacrylate compositions were converted to colored-cure indicating compositions by adding a dye masterbatch to each.
- the dye masterbatch was prepared by first formulating a 10 wt% dye base solution of Michler's hydrol in ethyl acetate and a 10 wt% acid solution of triflic acid in PROl.
- the 10 wt% dye base solution contained 1.35 part ("pt") ethyl acetate and 0.15 pt Michler's hydrol.
- the acid solution contained 1.8 pt PROl and 0.2 pt triflic acid.
- the dye masterbatch was prepared by combining 9.4 pt PROl, 0.366 pt 10% triflic acid solution, and mixing well, before adding 0.3 pt 10% dye base solution and mixing to complete the preparation and obtain a dye masterbatch having an acid/dye mol ratio of approximately 2.2/1 which contained approximately 3000 ppm dye.
- the final samples were made by combining, in a HDPE bottle, 0.25 pt of the dye masterbatch with 10 pt of the commercial cyanoacrylates shown in Table 1 to provide samples having a final dye content of approximately 75 ppm.
- Comparative Example 1 demonstrates that upon cure, pentamethoxy red (PMR), one of the dyes of US 2004/0254272 Al, does not bleach to a colorless form when employed as shown in Example 1.
- PMR pentamethoxy red
- a 2% solution of PMR in ethyl acetate was prepared and 0.25 pt of this PMR solution was added to 9.75 pt PROl to provide solution PMR- CA containing approximately 500 ppm PMR dye in PROl .
- sample PMR-CA thickened considerably, in 30 minutes was completely gelled, and in 2 hr was solid. This result shows that such a solution can not be made without adding a complementary charge of acid to the system for stability purposes.
- a PMR dye concentrate masterbatch was made by stabilizing PROl with triflic acid prior to introducing the PMR dye.
- a 10% PMR solution, PMR-10 was prepared by combining 1.35 pt methyl acetate and 0.15 pt PMR.
- PRO 1 , TFMSA Concentrate, and PMR- 10 were combined in a ratio 9.58 pt to 0.165 pt to 0.3 pt respectively to create a dye concentrate, PMR-3000, having an acid/dye molar ratio of approximately 1.5/1 and containing approximately 3000 ppm dye.
- the acid concentrates prepared in Table 2 were mixed with PROl and dye base concentrate A in the proportions (in parts by weight) shown in Table 3 to prepare dye masterbatches. This was accomplished by adding the acid concentrate to PROl in a HDPE bottle and mixing well for 15 minutes on a rotary agitator prior to introducing the dye concentrate. Following the addition of dye base concentrate the samples were placed back on the rotary agitator and allowed to mix at ambient temperature. All of the samples were charged to provide a dye concentration of approximately 3000 ppm and an acid/dye mol ratio of approximately ⁇ 2/1, with the exception of trifluoromethanesulfonic anhydride which had a 1/1 anhydride/dye mol ratio.
- Comparative Examples C2A- Master through C2G-Master had all either solidified or gelled, and thus were discarded.
- the anions of the acids alone are too nucleophilic, and therefore cause gelling.
- Comparative Examples C2C- Master through C2F-Master containing water, when compared to 2D-Master containing about 40% water, which did not cause gelling, it is apparent that the anions of the acids employed in MastersC2C-Master through C2F-Master were the causes of gelling, not the water content.
- C2G-Master although slightly acidic, it fails to stabilize the dye, in contrast to its imide acid, 2E-Master.
- C2I-Master With respect to C2I-Master, it is considered to closely resemble C2H-Master with respect to nucleophilicity of its anion. It is expected that other fluorine-free organic sulfonic acids will be equivalent to these in anion nucleophilicity.
- the remaining dye masterbatches were all deep blue colored fluids and were further employed to formulate colored cure indicating cyanoacrylate compositions by mixing 0.25 pt dye masterbatch with 9.75 pt PROl, as described in Example 1 to provide samples having a final dye content of approximately 75 ppm.
- the resulting samples were divided into equal portions in separate HDPE bottles and one aged at ambient conditions and the other at 49°C. As the samples aged, qualitative viscosity observations were made to determine if viscosity was stable or increasing, by inverting the bottle and observing the adhesive flow. Color of the samples was also monitored during aging, as described in the Test Methods section of this document. The viscosity and color assessment results are shown in Tables 4 through 7. Set time data was monitored periodically and results obtained reported in Table 8.
- This example examines stability of a series of color change cyanoacrylates containing various ratios of triflic acid and methanesulfonic acid.
- Two dye masterbatches were prepared employing the components and quantities (in parts by weight) shown in Table 9 to provide samples having acid/dye mol ratio of approximately 2/1 and containing approximately 3000 ppm dye. These dye masterbatches were then blended with each other to provide the mol ratios of triflic acid content shown in Table 10 (in parts by weight).
- This example examines the effect of accelerant on the set time and bleaching speed of a color change cyanoacrylate.
- 0.13 g dye masterbatch 3E- Master having acid/dye mol ratio of approximately 2/1 and containing approximately 3000 ppm dye Michler's hydrol cation, was added to a 5 g bottle of ScotchTM Super Glue Liquid and mixed well to obtain a deep blue colored sample containing approximately 75 ppm dye.
- the set time of this color change cyanoacrylate and an ADl 10 control were measured as described in the Test Method section with the exception that the test was conducted on LexanTM polycarbonate.
- PC polycarbonate
- ProntoTM Surface Activator by depressing the spray bottle pump mechanism one time, and allowing the accelerator to dry for a few minutes. Cyanoacrylate was applied to the uncoated coupon and the bond was closed immediately. A set time of 3-4 seconds was recorded with the sample bleaching colorless immediately upon cure. In this case the bonded area was clear and did not exhibit the cloudy appearance observed above when no accelerator was employed.
- the above findings show that by employing an appropriate accelerant, the set time and bleach speed on PC of colored cure indicating of the present disclosure can be reduced from many minutes to a matter of seconds.
- This example examines the effect of dye concentration on set time and color stability of cyanoacrylate gel.
- the components employed to prepare the samples of this composition were dye masterbatch 3E-Master, having acid/dye mol ratio of approximately 2/1 and containing approximately 3000 ppm Michler's hydrol cation, and CA-50 gel, used in the proportions (in parts by weight) shown in Table 12.
- Sample 5D consisted of 1 pt sample 5 A and 8 pt CA-50 gel and provided a dye content of approximately 5 ppm.
- the samples were formulated by hand mixing, with a spatula, the appropriate ratio of gel and dye masterbatch, and transferring the homogenous blue colored cure -indicating gel to a polypropylene container. Sample color and set time were assessed using the tests described in the Test Methods section and are presented in Table
- the masterbatches of Table 13 were further formulated with PROl to provide the color change cyanoacrylates of Table 14 by combining 0.25 pt masterbatch with 9.75 pt PROl, as described in Example 1, to obtain samples containing approximately 75 ppm dye. Color and set time of the samples were assessed as described in the Test Methods section and are reported in Table 14. Table 14 - Add/Dye Ratios
- This Example examines the effect of dye concentration on set time, color, and bleaching of color change cyanoacrylate compositions.
- a dye masterbatch consisting of PROl, triflic acid, and Michler's hydrol was prepared by the procedure described in Example 1, employing 9.43 pt PROl, 0.333 pt TFMSA Concentrate, and 0.3 pt dye base concentrate A, to obtain dye masterbatches having an acid/dye mol ratio of approximately 2/1 and containing approximately 3000 ppm dye.
- the dye masterbatches were further formulated with PROl to provide the color change cyanoacrylates of Table 15 using the proportions (in parts by weight) disclosed therein.
- Example 8 contained the bleachable dye of Michler's hydrol and the non-indicator dye 1,8-dihydroxyanthraquinone.
- Example 9 contained two color-change dyes, that of Michler's hydrol, and methyl yellow (4-(dimethylamino)azobenzene).
- Example 8 employed two different dye solutions.
- the bleachable dye solution was 3E-Master, containing triflic acid and Michler's hydrol in PROl having an acid/dye mol ratio of 2/1 and a dye content of 3000 ppm.
- the non-bleachable dye solution contained 38.92 pt SB20 and 1.2 pt of a 10% solution of 1,8-dihydroxyanthraquinone in methyl acetate, to provide a non-indicating dye content of approximately 3000 ppm.
- Example 9 employed two different dye solutions, both of which contained indicating dyes.
- the first dye solution consisted of the Michler's hydrol cation masterbatch of Example 1 based on PROl, triflic acid, and Michler's hydrol, and had an acid/dye mol ratio of approximately 2.2/1 and a dye content of approximately 3000 ppm.
- the second dye solution was prepared as in Example 1 by combining 9.25 pt PROl, 0.2 pt TFMSA Concentrate, and 0.6 pt of a 5% solution of methyl yellow in methyl acetate to provide a methyl yellow dye concentrate having an acid to dye mol ratio of 1/1 and a dye content of 3000 ppm.
- the adhesive composition was prepared by combining 8.08 pt PROl, 0.25 pt
- This example demonstrates that a medical grade butyl cyanoacrylate adhesive can be converted to a color change adhesive composition by addition of a Michler's hydrol dye masterbatch.
- the dye masterbatch and color change cyanoacrylate adhesive were prepared as described in Example 1 by first formulating a 10 wt% dye base solution of Michler's hydrol in methyl acetate and a 10 wt% acid solution of triflic acid in NexcareTM Drops Liquid Bandage (NDLB).
- the 10 wt% dye solution contained 1.35 pt methyl acetate and 0.15 pt Michler's hydrol.
- the acid solution contained 1.8 pt NDLB and 0.2 pt triflic acid.
- the dye masterbatch contained 9.46 pt NDLB, 0.30 pt 10% triflic acid solution, and 0.30 pt 10% dye solution which resulted in a dye masterbatch having an acid/dye mol ratio of approximately 1.8/1 and a dye content of approximately 3000 ppm dye.
- the adhesive composition was prepared by combining 9.75 pt NDLB and 0.25 pt dye masterbatch to provide a color change medical grade cyanoacrylate adhesive composition containing approximately 75 ppm dye.
- This deep blue sample was tested for set time as described in the Test Methods section and provided a set time of approximately 3-4 seconds, which was the same as the parent NDLB adhesive.
- this cyanoacrylate-based adhesive progressed from an uncured state to a cured state in the set time test, the color changed from an initial deep blue color to colorless.
- a drop of this adhesive composition was applied to the skin of a human hand, spread with a cotton- tipped applicator to provide a thin uniform layer, and observed for color change and set time. In approximately 1 minute the adhesive bleached colorless and was dry to the touch.
- This example displays the Strength Ratio of a variety of acids with various nitrated aniline Acidity Indicators using the procedures described in the Test Methods section of this disclosure. The results are given in Table 16 and show the differentiation between workable and nonworkable acids in the instant invention.
- This example examines color change properties of various Michler's hydrol dye derivatives. Masterbatches of each dye are made by combining 0.44 pt 10% solution of TFMSA in PROl with 0.40 pt 10% solution of dye base in THF and mixing well, followed by the addition of 9.16 pt PRO 1. The resulting dye masterbatches are agitated slowly for 30 minutes to assure homogeneity. Combining 4.91 pt PROl with 0.094 pt dye masterbatch and agitating slowly for 30 minutes completes the preparation of color change cyanoacrylate samples. The resulting samples are tested by placing 1 drop of color change cyanoacrylate on a first glass microscope slide, placing a second glass slide atop the first and observing after 1 minute to detect cure and note any color change that occurred. Inspecting the samples for cure reveals that all samples cure. Table 17 provides the color change behavior.
- This Example examines the effect of acid/dye mol ratio on the behavior of color change cyanoacrylate adhesives.
- the acids examined were BF 3 : 2 CH 3 OH, BF 3 (AcOH) 2 , and imide acid at acid/dye mol ratios ranging from 1 :1 to 5 : 1.
- the acid/dye mol ratio was based on mols BF 3 , not mols of the BF 3 - complexes.
- Acid/dye masterbatches were formulated by preparing 10 wt% solutions of each acid in SB 14 and combining these acid concentrates with Dye Base Concentrate A and SB 14 in the ratios shown in Table 18. Specifically, Dye Base Concentrate A was added to acid concentrate and mixed well before SB 14 was added and mixed to complete preparation of the acid/dye concentrates. Mixing 0.25 parts of acid/dye concentrate with
- Sample 13-6 based on BF 3 : 2 CH 3 OH and having acid/dye mol ratio of 1 :1, gelled shortly after preparation
- Sample 13-11 based on imide acid and having an acid/dye mol ratio of 1 : 1 gelled sometime between 1 and 2 weeks while aging at room temperature.
- the color stability of the adhesives was assessed after aging them for various lengths of time at room temperature as shown in Table 19. For each acid, increased acid/dye ratios resulted in increased bleach times.
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Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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US82497006P | 2006-09-08 | 2006-09-08 | |
PCT/US2007/077679 WO2008030903A1 (en) | 2006-09-08 | 2007-09-06 | Color change cyanoacrylate adhesives |
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EP2069446A1 true EP2069446A1 (en) | 2009-06-17 |
EP2069446B1 EP2069446B1 (en) | 2010-03-17 |
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US (2) | US20090317561A1 (en) |
EP (1) | EP2069446B1 (en) |
JP (1) | JP2010502823A (en) |
KR (1) | KR101464781B1 (en) |
AT (1) | ATE461255T1 (en) |
DE (1) | DE602007005388D1 (en) |
WO (1) | WO2008030903A1 (en) |
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US20080060550A1 (en) * | 2006-09-12 | 2008-03-13 | Macdonald Gavin | Color changing skin sealant with co-acid trigger |
US20080145316A1 (en) * | 2006-12-14 | 2008-06-19 | Macdonald John Gavin | Skin coating with microbial indicator |
JP4605671B1 (en) * | 2009-12-25 | 2011-01-05 | 田岡化学工業株式会社 | Ethyl-2-cyanoacrylate adhesive composition |
EP2588512B1 (en) | 2010-06-29 | 2015-03-11 | 3M Innovative Properties Company | Color indicating epoxy resins and methods thereof |
JP5891615B2 (en) * | 2011-06-28 | 2016-03-23 | コクヨ株式会社 | Coated product and method for producing the coated product |
US20140154536A1 (en) * | 2012-12-04 | 2014-06-05 | Ford Global Technologies, Llc | Methods and devices for detecting venting of a battery cell |
JP5242847B2 (en) * | 2012-12-26 | 2013-07-24 | コクヨ株式会社 | Application product and application system |
JP6340073B2 (en) | 2013-06-19 | 2018-06-06 | イーエルシー マネージメント エルエルシー | Methods, compositions and kits for whitening skin pigmentation spots |
JP6203562B2 (en) * | 2013-07-31 | 2017-09-27 | 未来工業株式会社 | Wiring and piping material support |
US11446256B1 (en) | 2021-08-20 | 2022-09-20 | Advantice Health, Llc | Aqueous wound healing formulation |
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US3646135A (en) * | 1967-09-18 | 1972-02-29 | Minnesota Mining & Mfg | Urea dyes |
CH540329A (en) * | 1967-11-10 | 1973-08-15 | Intercontinental Chem Co Ltd | adhesive |
US4006018A (en) * | 1968-05-10 | 1977-02-01 | Minnesota Mining And Manufacturing Company | Copying in color |
US3874884A (en) * | 1971-10-27 | 1975-04-01 | Lamson Industries Ltd | Coating compositions |
US3776950A (en) * | 1971-11-26 | 1973-12-04 | Minnesota Mining & Mfg | N-cyanophosphinimides |
US3856552A (en) * | 1973-04-02 | 1974-12-24 | Minnesota Mining & Mfg | Color projection transparencies |
SE410229B (en) * | 1976-05-11 | 1979-10-01 | Kockums Chem | AQUATIC COMPOSITION WITH REGULATED PH SHIFT WHEN FREEZING, AND SET FOR ITS PREPARATION |
US4407960A (en) * | 1980-06-25 | 1983-10-04 | American Sterilizer Company | Visual chemical indicating composition for monitoring sterilization |
US4405750A (en) * | 1981-03-31 | 1983-09-20 | Sumitomo Chemical Company, Ltd. | Colored cyanoacrylate adhesive composition |
US4495509A (en) * | 1983-06-09 | 1985-01-22 | Moore Business Forms, Inc. | Microencapsulation by interchange of multiple emulsions |
DE3540594A1 (en) * | 1985-11-15 | 1987-05-27 | Henkel Kgaa | ADHESIVES BASED ON CYANACRYLIC ACID ESTERS |
US5652280A (en) * | 1991-11-12 | 1997-07-29 | University Of Georgia Research Foundation, Inc. | Anionic photoinitiation |
US5874616A (en) * | 1995-03-06 | 1999-02-23 | Minnesota Mining And Manufacturing Company | Preparation of bis (fluoroalkylenesulfonyl) imides and (fluoroalkysulfony) (fluorosulfonyl) imides |
US5554664A (en) * | 1995-03-06 | 1996-09-10 | Minnesota Mining And Manufacturing Company | Energy-activatable salts with fluorocarbon anions |
JPH10176142A (en) | 1996-12-18 | 1998-06-30 | Toagosei Co Ltd | Cyanoacrylate adhesive composition |
DE19751953A1 (en) * | 1997-11-24 | 1999-05-27 | Henkel Kgaa | Air-cured polymerisable compositions, especially adhesives |
US6528555B1 (en) | 2000-10-12 | 2003-03-04 | 3M Innovative Properties Company | Adhesive for use in the oral environment having color-changing capabilities |
US6544714B1 (en) * | 2001-08-16 | 2003-04-08 | Eastman Kodak Company | Nacreous photographic packaging materials |
US6689826B2 (en) * | 2001-09-14 | 2004-02-10 | Henkel Loctite Corporation | Curable cyanoacrylate compositions and method of detecting cure |
TW554027B (en) * | 2001-10-18 | 2003-09-21 | New Prismatic Entpr Co Ltd | Reversible thermochromic composition |
WO2003065841A1 (en) * | 2002-02-05 | 2003-08-14 | Henkel Corporation | Luminescing and/or fluorescing radiation-curable, cyanoacrylate-containing compositions |
US6877230B2 (en) * | 2002-02-22 | 2005-04-12 | Chris Tapia | Method and apparatus for cutting hair |
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US6835789B1 (en) * | 2003-06-18 | 2004-12-28 | Loctite (R&D) Limited | Cyanoacrylate compositions |
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US20080145316A1 (en) * | 2006-12-14 | 2008-06-19 | Macdonald John Gavin | Skin coating with microbial indicator |
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2007
- 2007-09-06 US US12/377,966 patent/US20090317561A1/en not_active Abandoned
- 2007-09-06 WO PCT/US2007/077679 patent/WO2008030903A1/en active Application Filing
- 2007-09-06 US US11/850,873 patent/US8217110B2/en not_active Expired - Fee Related
- 2007-09-06 AT AT07841916T patent/ATE461255T1/en not_active IP Right Cessation
- 2007-09-06 JP JP2009527550A patent/JP2010502823A/en not_active Withdrawn
- 2007-09-06 EP EP07841916A patent/EP2069446B1/en not_active Not-in-force
- 2007-09-06 DE DE602007005388T patent/DE602007005388D1/en active Active
- 2007-09-06 KR KR1020097004744A patent/KR101464781B1/en not_active IP Right Cessation
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WO2008030903A1 (en) | 2008-03-13 |
US8217110B2 (en) | 2012-07-10 |
DE602007005388D1 (en) | 2010-04-29 |
JP2010502823A (en) | 2010-01-28 |
EP2069446B1 (en) | 2010-03-17 |
US20080075862A1 (en) | 2008-03-27 |
US20090317561A1 (en) | 2009-12-24 |
ATE461255T1 (en) | 2010-04-15 |
KR20090048500A (en) | 2009-05-13 |
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